Asymmetrically disubstituted isoindolines

ABSTRACT

ISOINDOLINE DERIVATIVES ASYMMETRICALLY DISUBSTITUTED IN THE 1- AND 3-POSITIONS CORRESPONDING TO THE FORMULA   1-(R&#39;&#39;=),3-(R2=)ISOINDOLINE   IN WHICH THE CYCLIC RADICAL R IS ANAROMATIC RING, A SUBSTITUTED AROMATIC RING, A TETRAHYDROGENATED AROMATIC RING, A NITROGEN CONTAINING HETEROCYCLIC RING,OR A SULPHUR CONTAINING HETEROCYCLIC RING, AND R1 AND R2 WHICH ARE DIFFERENT, ARE BIVALENT RADICALS OF A COMPOUND WHICH CONTAINS TWO ACTIVE HYDROGEN ATOMS ATACHED TO A NITROGEN ATOM; AND A TWO-STAGE PROCESS FOR MAKING THE SAME. THE ISOINDOLINE DERIVATIVES ARE EXCELLENT DYESTUFFS FOR DYEING AND PRINTING SYNTHETIC FIBER MATERIALS.

United States Patent 3,794,659 ASYMMETRICALLY DISUBSTITUTED ISOINDOLINES Heinrich Leister, Cologne-Stammheim, and Heinrich Vollmann, Leverkusen, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing Original application Sept. 8, 1967, Ser. No. 666,458, now Patent No. 3,646,033. Divided and this application Sept. 8, 1971,,Ser. No. 178,826 Claims priority, applicatign Germany, Sept. 9, 1966,

F Int. or. com 59/02, 99/110 US. Cl. 260-305 1 Claim ABSTRACT OF THE DISCLOSURE Isoindoline derivatives asymmetrically disubstituted in the 1- and 3positions corresponding to the formula in which the cyclic radical R is an aromatic ring, a substituted aromatic ring, a tetrahydrogenated aromatic ring, a nitrogen containing heterocyclic ring, or a sulphur containing heterocyclic ring, and [R and R which are dilferent, are bivalent radicals of a compound which contains two active hydrogen atoms attached to a nitrogen atom; and a two-stage. process for making the same. The isoindoline derivatives are excellent dyestuffs for dyeing and printing synthetic fiber materials.

DISCLOSURE This application is a division of our co-pending application S.N. 666,458 filed Sept. 8, 1967 now US. Pat. 3,646,033.

The invention relates to novel isoindoline derivatives and to a process for producing such.

The novel isoindoline derivatives have the general formula:

- i" wherein the cyclic radical R is an aromatic ring, a substituted aromatic ring, 'a tetrahydrogenated aromatic ring,

a nitrogen-containing heterocyclic ring, or a sulphur-containing 'heterocyclic'ring and R and R are different When 1,3 diimino-isoindoline (II) is used, the process? according to the invention can be illustrated by the following reaction scheme:

N 3 -NH| C I H an radicals of a compound which contains two active hydroradicals ha ing botlivalences on a single carbon or nitrogen atom...

It has b e en, found that novelisoindoline derivatives are.

obtained when an isoindoline which contains easily exchangeable substituents in the 1- and 3-positions is first:

reacted with one compound which contains two active hydrogen atoms attached to a carbon or nitrogen atom,j

using not more than'l mole of the compound containing two active hydrogen atoms per mole of the isoindoline and carrying out the reaction at temperatures from 10 to 110 C., and subsequently reacting the resulting reaction product with at least an equimolar amount of a second, different compound containing two active hydrogen atoms attached to a carbon or nitrogen atom at temperatures from 80 to 220 C.

gen atoms attached to a carbon or nitrogen atom, the

radicals R and R being difierent.

Preferred R radicals include: (a) Malonic acid esters of preferably lower alcohols;

bivalent radicals of cyano-methyl derivatives of the structure in which A can be a nitrile group; carboxylic acid amide groups which can also contain alykl groups, hydroxyalkyl groups or--optionally substituted-aryl radicals on the nitrogen atom of the amide; carboXylic acid ester groups, the alkoxy radical of which can be derived from shortchain as Well as from long-chain, linear or.v branched alcohols; a -CO-alkyl or CO-aryl group; a heterocyclic ring system, eg an a-pyridyl or benzimidazole radi cal; an aryl radical which can also contain substituents, such as nitro groups or halogen.

(b) bivalent radicals of the general structure in which B denotes the. complement of a fiveor six- I ,membered isoor heterocyclic ring;

(c)-Imide radicals which are derived from primary amines of the heteroyclic series.

Preferred R radicals include:

(a) Any one of the bivalent radicals mentioned under (a) (c) for R provided that itis diflerent from the radical R introduced in the first reaction step;

(b) Imide radicals which are derived from a primary amine of the aliphatic or aromatic'series; and I (c) Hydrazone radicals of the general structure in which D and E denote hydrogen or a methyl group, D can be hydrogen and E can be an aryl radical which may Patented Feb. 26, 1974 be substituted by halogen atoms or nitro groups and D+E can denote the complement of a fiveor sixmembered hetero ring.

The isoindoline derivatives which contain easily exchangeable subs'tituents in the 1- and 3-positions and serve as starting material for the process according to the invention can be readily obtained by known processes, from such starting materials as o-phthalo-dinitriles, phthalic acid anhydride or phthalimide. Suitable isoindoline starting compounds include:

(a) The 1, 3-diim'ino-isoindoline (IV) which can also be present or react in tautomeric form as aminoiminoisoindolenine (V) for example, in the form of its salts with weak or stronger acids (cf. German patent specification No. 879,100):

(b') Monomeric alkoxy-isoindolenines and their alcohol addition products of the structure (VI) which are readily obtainable from phthalodinitrile by reaction in anhydrous alcohols and in the presence of an alkali metal alcoholate (cf. German patent specification No. 879,102)

Alk. ililk.

or with alkali metal alcoholates (cf. German patent specification No. 906,935)

(d) The reaction product of hydrogen bromide with phthalo-dinitrile in solvents such as glacial acetic acid, which, based on analysis and properties, can be assumed to be a dibromine hydrate of 1-bromo-3-imino-isoindolenine (VIII) (cf. FP 1,070,912)

(VIII) Compounds which can be reacted in succession with the isoindoline derivatives serving as starting materials (e.g. those of Formula II) or with the intermediates (e.g. those of the Formula III) include:

(a) Malonic acid dimethyl ester, malonic acid diethyl ester, malonic acid dinitrile, cyano acetic esters of the formula CN H2=C I wherein R is an ester radical which can be derived from a great variety of alcohols, such as methanol, ethanol, normal-, isoand tert.-butanol and amyl alcohols; from mixtures of C -C alcohols as can be industrially obtained by known syntheses; from alcohols of the fatty series such as lauryl alcohol or octadecanol; from cycloaliphatic alcohols such as cyclohexanol or menthol; from aliphatic alcohols which contain substituents, such as glycol monoalkyl ether, ethyelne-chlorohydrin, fi-cyanoethanol, [3- phenoxyor p-phenyl-mercaptoethanol, [i-phenylethylalcohol, 'y-phenylpropanol, 'y-phenyl-allyl alcohol; from benzyl alcohol and its substitution products, such as 4- methyl-, 2- and 4-chloro-, 3,4-dichloroor 2,4,6-trichloro-benzyl alcohols; or from alcohols containing heterocyclic rings, such as tetrahydrofurfur-alcohol; cyano acetamides of the formula the amide radicals of which can be derived from am monia and a variety of primary amines R =alkyl or aryl radical) or secondary amines (R and R =allyl or aryl, or R and R form 5- or 6-membered rings with the nitrogen), such as methyl-, ethyl-, butyland higher paraffin-amines, aniline, p-toluidine, monoand polychloroanilines, -methoxyand -y-dimethy1- amino-propylamine and monoor dihydroxyethylamine; li-cyano ketones of the formula in which R can denote a methyl or phenyl radical, such as cyano-acetone and w-cyanoacetophenone; benzyl cyanide and derivatives thereof substituted in the 2-, 3- and/or 4-positions by fluorine, chlorine or bromine, as well as 3- and 4-nitrobenzyl cyanide; acetonitriles carrying heterocyclic substituents and having the formula hetero ring such as pyrazolyl- (3 -acetonitrile,

imidazolyl- (4) -acetonitrile, 2-cyanomethyl-benzimidazole, l-methyl-2-cyanomethyl-benzimidazole, 1-}8hydroxyethyl-2-cyanomethyl-benzimidazole, 1-fl-cyanoethyl-2-cyanomethyl-benzimidazole, 2-cyanomethyl-1H-naphth[2,3-d] -imidazole, l-methyl- 1 ,2,3triazolyl- 4) -acetonitrile, 2-phenyl- 1 ,2,3-triazolyl- (4 -acetonitrile,

5 -phenyl- 1 ,2,3-triazolyl- (4 -acetonitrile, tetrahydrobenzo-l,2,3-triazolyl-(1)-acetonitrile, 4-phenyl-1,2,4-triazolyl- (3 )-acetonitrile, isoxazolyl- (3 )-acetonitrile, Z-cyanomethyl-benzoxazole,

thiazolyl- (4) -acetonitrile,

2-methylthiazolyl- (4) -acetonitrile, 2-cyanomethylbenzothiazole, pyridyl- (2 -acetonitrile,

pyridyl- (3 -acetonitrile,

pyridyl- (4 -acetonitrile,

quinolyl- (2) -acetonitrile, quinazolyl- 2) -acetonitrile, or quinoxalyl- (2) -acetonitrile;

(b) 5- or 6-membered isoor heterocyclic ketomethylene compounds having the formula or hydroxy compounds capable of reacting like ketoa methylene compounds, such as:

3-methyl-pyrazolone- 1-phenyl-3-methyl-pyrazolone- (5 1,2-diphenyl-3,5-dioxopyrazolidine, indoxyl,

N-methyl-indoxyl,

oxindole, N-methyh and N-ethyl-oxindole, barbituric acid, 3-hydroxy-thionaphthene, 2,4-dioXo-1,2,3,4-tetrahydroquinoline, N-methyl-2,4-dioxo-1,2,3,4-tetrahydroquinoline, resorcinol,

dihydro-resorcinol,

phloroglucine, or 1,3-diketohydrindene;

(0) Primary amines of the heterocyclic series, such as:

1-phenyl-3-methyl-5-amino-pyrazole,

Z-amino-benzimidazole,

1-methyI-Z-amino-benzimidazole,

Z-amino-benzoxazole,

2-amino-S-nitro-benzoxazole,

2-amino-4pheny1-thiazole,

2-amino-4-methyl-5-carbethoxy-thiazole,

2-amino-benzothiazole,

2-amino-6-methoXy-, -6-ethoxyand -6-dimethylaminobenzothiazole,

3-amino-1,2,4-triazole,

3-amino-5-carbethoxy-1,2,4-triazole,

2-amino-1,3,4-oxdiazole,

2-amino-5-cyclohexyl-, -5-benzy1- and 5-y-pyridyl-l,3,4-

oxdiazole,

2-amino-5-phenyl-1,3,4-oxdiazole,

5-amino-3-phenyl-1,2,4-thiadiazole,

Z-amino-S-phenyl-1,3,4-thiadiazole,

S-amino-sulpholane,

2-amino-pyridine.

Compounds which can be reacted with the intermediates (e.g. of the Formula III) include:

(a) Primary amines of the aliphatic or aromatic series, such as methyland ethylamine, Z-hydrQXy-ethylamine, ethylene-diamine and -dimethylamino-propylamine, benzylamine, aniline, 0-, mand p-toluidine, xylidines, mesidine, 2,3- and 4-chloroor alkoxy-am'lines, 3-nitroaniline, 3- and 4-amino-acetauilide or -benzanilide, N- monophthalyl-p-phenylene-diamine, 3- and 4-aminobenzoic acid, 3- and 4-cyanonaniline, S-amino-benzamide or -benzanilide, 3-amino-benzene-sulphonamide, 2-phenyl- 5-amino-benzotriazole-( 1,2,3

(b) Hydrazines with a free NH group, such as hydrazine, 1,l-dimethyl-hydrazine, phenylhydrazine, haloand nitro-phenyl-hydrazine, N-amino-piperidine, N:

6 amino-morpholine, N-amino-2-methyl-2,3-dihydro-indole, N-amino-l,2,3,4-tetrahydro-quinoline.

For the production, according to the invention, of the isoindoline derivatives of the General Formula I which are asymmetrically disubstituted in the 1- and 3-positions, it is advantageous to obtain the monosubstituted intermediates, e.g. products of the Formula III, in the purest form possible. In order to achieve this, it is desirable to carry out the reaction of the starting materials with the compounds of the type at a relatively low temperature, since otherwise symmetrically disubstituted isoindolines may be easily formed. The temperature to be chosen in the first reaction step depends, apart from the solubility of the components and particularly of the resultant intermediate in the solvent used, to a high degree on the activity of the compound used. With highly reactive cyanornethyl compounds, such as malonic dinitrile or cyanoacetic ester, the starting material can be reacted at room temperature and below to form intermediates of the type of Formula III, Whereas with more Weakly activated methylene groups and heterocyclic amines the reaction temperature can be raised to 60 to C., without a bilateral reaction occurring. If highly reactive cyanomethyl compounds are used, it may also be expedient to use less than 1 mole of the component per mole of the isoindoline used as starting material (e.g. only 80% of the theoretical amount), since unreacted isoindoline is, in most cases, substantially more readily soluble than the corresponding monoreaction product (III) which separates and can be easily isolated in pure form by filtering off with suction. The production and properties of a number of monoreaction products of the type (III) are described in the following examples. These products have hitherto been unknown.

As solvents for the reaction of the first reaction step (e.g. [II] [111]), there are preferably used alcohols in which the starting materials are readily soluble, such as methanol, ethanol, propanols, butanols, glycols and glycol monoethers or diglycol monoethers, further acid amides, such as formamide or dimethyl formamide. In the case of the 1,3-diimino-isoindoline which readily dissolves in water at 20 to 35 0, even Water or a mixture of water and alcohol can be useful as a solvent. An addition of ammonia-binding agents may be expedient, especially if the starting materials contain groups which easily react with ammonia, such as carboxylic ester groups.

For the second reaction step (III)- (I), which necessitates higher temperatures of about 80 C. to about 220 C., the same solvents as mentioned above can be used, or, preferably, high-boiling alcohols or other high-boiling solvents, such as aromatic hydrocarbons (e.g. toluene, xylene) and their derivatives (e.g. nitroor chlorobenzenes), pyridine, quinoline or pyrrolidones. In both reaction steps the amountof solvents used is so chosenor so adjusted during the reaction by partially distilling olf or adding solvent-that the reaction product is present after completion of the reaction in a readily stirrable suspension. In general, there are therefore preferably used about 4 to about 10 parts by volume, referred to parts by weight of the starting material concerned. The process according to the invention enables the hitherto unknown isoindolines of the General Formula I which are symmetrically disubstituted in the 1- and 3-positions, to be produced with good yields and a high degree of purity.

The isoindoline derivatives which can be obtained according to the present process are eminently suitable for the dyeing and printing of synthetic materials made of, for example, polyester, polyamide, cellulose triacetate and also polyacrylonitrile, which they dye in greenish yellow to red shades of good to very good fastness to wet processing, sublimation and thermofixing and good to excellent fastness to light. The afiinity can sometimes be improved by mixing individual dyestulfs or also by halogenation. Some of the isoindolonines prepared according to the invention are also interesting as pigment dyestuifs.

In the following examples the parts are parts by weight and the percentages are percent by weight, unless otherwise stated.

EXAMPLE 1 (a) 133 parts 2-amino-benzimidazole (1 mole) and 200 parts of 88% 1-amino-3-imino-isoindolonine (1.2 moles) are stirred in 400 parts by volume formamido at 70 C. for about hours. The reaction product which crystallizes in the form of yellow needles is filtered off with suction after cooling and thoroughly washed with water to remove the amino-imino-isoindo1onine used in excess. After drying at 60 C. in a vacuum, the yield of 1 [benzimidazolyl (2) imino] 3-imino-isoindoline amounts to about 220 parts corresponding to 84% of theory. The mono-substitution product melts at 350- 354 C. with decomposition. It dissolves in dilute acetic acid with a yellow color. It forms with phenyl-hydrazine in a glacial acetic acid solution a phenylhydrazone of MP. 220225 C. (decomp.), which crystallizes in the form of reddish yellow needles.

(b) 13 parts 1-[benzimidazolyl-(Z')-imino]-3-iminoisoindoline obtained according to Example 1(a) and 6 parts cyanoacetic acid ethyl ester are stirred in 100 parts by volume nitrobenzene at 8090 C. for 3-4 hours, while ammonia escapes. If no more starting material can be detected by chromatography, the mixture is allowed to cool, the reaction product which crystallizes in the form of orange-yellow needles is filtered off with suction, washed with methanol and dried at 90-100 C. There are obtained about parts l-[benzimidazolyl-(2)-imino]- 3- (cyanocarbethoxy) -methylene] -isoindoline corresponding to 84% of theory of MP. 278279 C. (decomp.). The dyestufi dissolves in concentrated sulphuric acid with a yellow color, in a methanolic sodium hydroxide solution with a red-orange color.

EXAMPLE 2 (a) 10 parts of strand material of polyethylene glycol terephthalate are dyed at 9698 C. for two hours in a bath consisting of 600 parts of water, 0.1 part of the dyestufi of Example 1(b) in finely divided form, 3.4 parts of a mixture of o-, mand p-cresotic acid methyl ester and 0.6 part of a mixture of equal parts of aralkyl-sulphonate and a non-ionic polyglycol ether, after sulphuric acid had been added until a pH value of 4.5 was obtained. The material is subsequently rinsed and dried. A clear reddish yellow dyeing of good fastness to washing and sublimation and excellent fastness to light is obtained.

(b) 10 parts of loose material of polyethylene glycol terephthalate are dyed at 120-130" C. for 2 hours in a bath at pH 4.5 consisting of 400 parts water and 0.15 part of the dyestuff of Example 1(b) in very finely divided state, as well as of 0.3 part of a mixture of equal parts of an aralkyl-sulphonate and a non-ionic polyglycol ether. After rinsing and drying, a clear reddish-yellow dyeing is obtained.

(c) A fabric of polyester fibre material prepared from terephthalic acid and 1,4-bis-hydroxymethyl-cyclohexane is impregnated on a foulard with a liquor containing, in 1000 parts of water, 20 parts of the dyestuif of Example 1(b) in a very finely divided state, as well as 10 parts of a conventional thermosol auxiliary, particularly a polyethylene ether. The fabric is then squeezed to a weight increase of 70% and dried at to 120 C. It is subsequently treated for about 45 seconds at 180-220" C. with hot air, rinsed, reductively after-treated in known manner, if desired, and dried. A clear reddish yellow dyeing of good fastness to rubbing and sublimation and excellent fastness to light is obtained with a dyestulf yield of almost (d) If in Example 2(a) the fabric of polyester material is replaced with a fabric of cellulose triacetate and the process is otherwise carried out as described, then there is obtained a somewhat greenish yellow dyeing of very good fastness to washing and sublimation and excellent fastness to light.

(e) 10 parts of strand material made of a polyamide (prepared by condensation of caprolactam) are slowly heated to boiling temperature in a bath containing, in 400 parts of water, 0.2 part of the finely divided dyestufi prepared according to Example 1(b) and 0.2 part of a conventional dispersing agent, and dyed at the boil for 1 hour. A clear reddish yellow dyeing of very good fastness to water and good fastness to washing and light is obtained.

EXAMPLE 3 104 parts l-benzimidazolyl-(Z')-imino]-3-imino-isoindoline prepared according to Example 1(a) and 32 parts malonic dinitrile are introduced into 1600 parts by volume nitrobenzene and the mixture is stirred at 80 C. for 2 hours. The 1-[benzimidazolyl-(2')-imino]-3-(bis cyanomethylene)-isoindoline which crystallizes in the form of orange-colored needles is filtered oil with suction after cooling and washing with nitrobenzene and cyclohexane. The yield amounts to about parts corresponding to 97% of theory; M.P. 3l3315 C. (decomp.). On polyester fibres a clear intense orange dyeing of good fastness to sublimation and excellent fastness to light is obtained according to Example 2(a) and 2(b), on cellulose triacetate fibres a yellow dyeing fast to light and exhaust fumes is obtained according to Example 2(d), and the dyeings on polyamide fibres according to Example 2(e) are red-orange.

In analogy with Examples 1(b) and 3, the cyanoacetic acid esters stated in the following table can also be reacted with 1- [benzimidazolyl- (2 -imino] -isoindoline, whereby dyestuffs are obtained, which dye polyester, triacetate and polyamide fibres according to Example 2(a) to 2(e) in clear reddish yellow shades of very good fastness properties.

R In Yield, Example NC-CH -COOR percent M.P. C.)

4 -C4H9(l1) 73 188-190 9 -CH;CHOH 71 259-261 -omcm-o EXAMPLE 11 A mixture of 70% of the dyestutf prepared according to Example 7 and 30% of the dyestufi prepared according to Example 5 is thermosolized according to the instructions of Example 2(c). A brilliant golden yellow dyeing of very good fastness to sublimation and rubbing and excellent fastness to light is obtained with a dyestuflt yield of about 91%.

Brilliant golden yellow dyeings of very good fastness properties are also obtained with mixtures of the dyestufls of the following examples:

Dyestut! yield, Fastness 1 0 EXAMPLE 12 5.2 parts 1-[benzimidazolyl-(2)-imino] 3 imino-isoindoline (Example 1a) and 2 parts cyanoacetamide are heated in 30 parts by volume nitrobenzeue at 150-l60 C. for 10 minutes. Ammonia evolves already during heating up, and l-[benzimidazolyl-(2')-imino]-3-[(cyano-carbonamido)-methylene]-isoindoline crystallizes after a shot time in the form of yellow-orange short rodlets. The prodnot is filtered off with suction after cooling and washed with methanol. The dyestuif (yield about of theory, M.P. 322-323 C. with decomp.) dyes polyester fibre material according to Example 2(c) in yellow-orange shades.

In a similar manner, 1-[benzimidazolyl-(2)-imino]-3- imino-isoindoline (Example 1a) can also be reacted with the active methylene compounds stated below and the aromatic and 'heterocyclic amines of the general structure Mixture percent to light H 70% Example 10 plus 30% Example 6-- 87 Excellent. 35 73% Example 10 plus 30% Example 8 Do. 7 0 Example 8 plus 30% Example 6- 87 Do. 90% Example 6 plus 10% Example 8 88 Do. H

Dyeing R according V H 7 Yield, to exam- Example v Solvent temperature C.) percent ple Shade 1a Nitrobenzene (10o) 81 2(1)) Reddlsh NC-CHz-CONH CH; 2(0) yellow.

14 rec-oni-co-mcmomom, -i-- .'ao- 7a D0.

c 15 CuH:C0CH:-CQOC:H& -.---dO.L 64 2(a) Somewhat 4 2(b) reddish 2(0) yellow.

IB....- H -----d0 -2 64 2(0) Yellow-orange.

NC-CHr-C 17;; NC-CHz-C-Ifii Without solvent (200-220).-- 53 22%)) Yellow.

' E0 on 1B paminobenzolc acid ethyl 64 2(a) v Do.

HgN C O 0 01H; ester (200), 2(b) 19 HCIi-CHa Nitrobenzene 71 2(0) Reddish yellow.

1' C011: 20 "I: Nitrobenzene (18 60 2(0) D0.

HaN-C /CH 21 N--C-CH; lsobutanol plus a little s1 2(a) Do.

g H glacial acetic acid 2(b) HzN- C--C 0 0 C111; (2c) TABLECoutinued Dyeing R according Yield, to exam- Example H Solvent temperature C C.) percent ple- Shade 22 N Nitrobenzene (120) 62 2(b) Somewhat 2(c) reddish yellow. HzNC S 23 /N .-....do 61 2(0) Orange-yellow.

HaN-O 24 NN ----do 73 2(a) Yellow.

' I! ll 2(b) HzN-O C-(LH; S

EXAMPLE 25 25 The solutions of 4 parts l,1-dimethoxy 3 iminoisoindoline in parts by volume methanol and of 3.2 g parts Z-cyanomethyl-benzimidazole in 20 parts by volume methanol are combined whereupon a deep reddish yellow mixture is formed. The separation of yellow rhombs The l [(cyano-benzimidazolyl 2') methylene1-3- imino-iso-indoline used as starting material in Example 25(d) can be obtained by the following 3 processes 25(a) to 25(0):

(a) A solution of 16 parts 2-cyanomethyl-benzimidazole (0.1 mole) in 100 parts by volume methanol is rapidly poured into a previously prepared solution of 30.6 parts of 95% l-aminO-3-imin0isoindolenine (0.2 mole) in 400 parts by volume methanol. The mixture acquires a deep yellow color and separation of the monoreaction product in crystalline form begins during the heating up to boiling temperature. The mixture is heated under slight reflux for 1 hour, then cooled to 25-30 C., the product is filtered olf with suction, washed with methanol and-in order to completely remove the excess l-amino 3 imino-isoindolenine-washed thoroughly with water. After drying at 60 C. in a vacuum, the l- [(cyanobenzimidazolyl 2') methylene] 3 imino-isoindoline (yield 28 parts corresponding to 98% of theory, referred to 2-cyanomethyl-benzimidazole) is a loose, golden-yellow, finely crystalline powder which is readily soluble in cold glacial acetic acid. It crystallizes from dimethyl formamide upon the addition of methanol, in the form of yellow rhombs which become dark-colored on heating to 280 C. but do not melt up to 330 C. A sample dipped at 345-350" C. turns dark within one minute, sinters and melts with the evolution of gas. When heated with phenyl-hydrazine in a glacial acetic acid solution, the monoreaction product forms a phenylhydrazone (orange-red needles) which melts at 256- 258- C. with decomposition, after recrystallization from a mixture of toluene and nitro-benzene. With hydrazine hydrate in methanol at 60 C., there is formed a hydrazone which dissolves in glacial acetic acid and concentrated sulphuric acid with a yellow color and in a methanolic sodium hydroxide solution with a deep yelloworange color and does not melt up to 360 C.

begins after about 10 minutes. To complete the reaction, the mixture is stirred at 60 C. for one hour, then cooled to room temperature, the product is filtered off with suction, washed with methanol and dried at 60 C. in a vacuum. The crude yield amounts to 5.8 parts corresponding to 100% of theory. 'For purification the product is dissolved in dimethyl formamide at C., filtered ofi from a red byproduct (0.25 part 1,3 bis [(cyanobenzimidazolyl 2') methylene] isoindoline) and precipitated with methanol. -It is filtered off with suction after cooling, washed with methanol and thoroughly dried at C. The reaction product (about 4 to 4.5 parts) is identical with the product obtained according to 25 (a) in respect of appearance (-yellow rhombs), properties, melting point and analysis.

(0) 24.5 parts 1-piperidino-3-iminoisoindolenine are dissolved in 50 parts by volume methanol and the solution is combined at room temperature with a solution of 15.7 parts Z-cyanomethyl-benzimidazole in 50 parts by volume methanol. In a weakly exothermic reaction the crystallization of yellow rhombs begins after about one minute, and piperidine is eliminated. The mixture is stirred at room temperature for about 3 hours, then suction-filtered, the filter cake is washed with methanol and dried at 80 C. The reaction product (yield about 27 to 28 parts) can be recrystallized from dimethyl formamide-l-methanol. It yields with phenyl-hydrazine in a glacial acetic acid solution the phenyl-hydrazone of MP. 256258 C. (decomp.) which is also obtained according to 25 (a).

(d) 50 parts 1 [(cyano benzimidazolyl 2')-methylene] 3 imino-isoindoline and 15 parts malonic dinitrile are introduced into 1000 parts by volume nitrobenzene and the mixture is heated with stirring at C. for one hour and then at 210 C. for a short time, whereupon a deep orange-colored solution is formed with the evolution of NH;.,. The resultant l-[(cyano-benzimidazolyl 2') methylene] 3 (bis cyano methylene)- isoindoline crystallizes upon cooling in the form of orange-colored needles. It is filtered off with suction, washed with nitrobenzene and methanol, and after drying there are obtained about 52 parts of the dyestuff, corresponding to 89% of theory (M.P. 360 C.). The dyestuif dissolves in a methanolic sodium hydroxide solution with a red-orange color. Polyester fibres are dyed according to Example 2(a) to 2(c) in brilliant yellowish dish orange shades.

By a process similar to that described in Example 25 (d), 1 [(cyano benzimidazolyl 2') methylene]- 3-imino-isoindoline can be reacted with other active methylene compounds, with hydrazines :and with aromatic and heterocyclic amines of the general formula (used in equimolar amounts), as can be seen from the following table.

Dyeing Yield, according Example Solvent temperature C 0.) percent to Ex.- Shade 26 N CCH:COO-C;H Nitrobenzene (140) 92 2(0) Yellow-orange.

nc-cm-ooo-om-Q (c) '.....d0 83 2 D NC-CHr-COO-(CHzh-Q 29. Benz anide 200 ..':::.::7; 56 2 c Ora eellow.

y Y s y 30... "7:52: H:C3-(|'JC Nitrobenzena (120) 92 2(0) Red.

If CHI 31. .72-:2: Aniline (l85)..-:'...-:-::;:: 73 2(b) Reddish yellow.-

HsN 2(0) 32. Amine-benzolo acld ester 66 2(b) Do.

E G-000cm (200).

33. .TJ--:T. Nitrobenzene (l80).;::::r::::= 84 2(8) Golden yellow.

34- 32410-. --'.T-T;I:;I:::2:II';: 84 2(0) D0.

HsN

NHC O CH:

- -221: N :2; .do. .rzzzzzzzzz: 76 12(6) Yellow-orange.

/N--C! I 36- HzN-N HaC Ethylene glycol (190) Do.

37. HC(|'f-CH: Ethyleneglycol (180-200) 62 2(0) Reddish yellow HzN- N N ls l I 33. -7: r Nitrobenzene (180) 96 2(0) Yellow.

H:N /&H

N H I 39 21:: .60. -:::::.T;: 2(0) Red-orange.

mcio (XI? HzN-(f S 40. /N 7:; .d0. 89 2(6) Orange.

HaN-C 41- IET-CF-C H r.:. 4110-- .:'.:-::r;:.:.r.:.-.: 86 2(0) D0.

H:NC (E-GOOCaHI l EXAMPLE 42 I! N-CHaCH: O H

8 parts 1 [cyano benzimidazolyl 2) methylene]- 3-irnino-isoindoline (Example 25a) are introduced into 100 parts by volume B-aminoethanol and the mixture is stirred at 80 C. for /2. hour, whereupon the form of the crystals changes. The mixture is diluted with methanol, the product is filtered 05 with suction after. cooling, and washed with methanol and water. According to analysis, the product of the above structural formula has been formed. In contradistinction to the starting material, the product is precipitated from its solution in a methanolic sodium hydroxide solution by means of water. The yield amounts to about 8 parts corresponding to 86.5% of theory.

EXAMPLE 43 10 parts of polyacrylonitrile fibre in the form of strands are introduced at 50 C. into a dyebath of 400 parts of water containing 0.05 parts of the dyestutf obtained according to Example 42, 0.'l5 parts of 80% acetic acid, 0.2 parts sodium acetate, and 0.4 parts of a condensation product of a higher alcohol with ethylene oxide, for example, the condensation product obtained from 1 mole olefin alcohol and moles ethylene oxide. The temperature of the dyebath is raised to boiling point within minutes and dyeing is continued at this temperature for one hour. The dyebath is then very well exhausted. An intense yellow dyeing of excellent fastness to light is obtained.

EXAMPLE 44 NC-C-C 3 parts 1-[(cyano-benzimidazolyl 2') methylene]-3- iminoisoindoline (Example a) and 80 parts by volume of a methylamine solution are heated with stirring at 60 C. for V2 hour. After cooling, the mixture is diluted with some water, the product is filtered off with suction and washed with water and then with 50% methanol. In contradistinction to the starting material, the reaction product (yield about 2.6 parts corresponding to 83% of theory) can be precipitated from its solution in methanolic sodium hydroxide by means of water. It dyes polyacrylonitrile fibres according to Example 43 in intense yellow shadesof excellent fastness to light.

16 EXAMPLE 4s NC-(fi-C O CH:

(a) A solution of 11 parts of a mixture of about S-methyl-isoxazole with about 20% 3-m'ethyl-isoxazole in 50 parts by volume methanol is mixed at a maximum temperature of 50 with 8 parts of a 40% aqueous sod ium hydroxide solution, while stirring. As is known, the 5- methyl-isoxazole is thereby split off rather smoothly to form monocyano-acetone, whereas the 3-methyl-isoxazole remains unchanged, so that an alkaline methanol solution is formed which contains about 8.3 parts monocyano-acetone. (The mixture of about 80% 5- and about 20% 3- methyl-isoxazole is most conveniently prepared according to the instructions given by C. H. Eugster, L. Leichner and E. Jenny, Helv. 46, S63564 (1963) from a-ketobutyraldehyde-dimethyl-acetal with hydroxylamine chlorine hydrate. The said publication also contains references to the smooth splitting of S-methyl-isoxazole with alkali to form monocyano-acetone according to older literature references.)

The freshly prepared cyano-acetone solution so obtained is immediately stirred at room temperature into a previously prepared-solution of 14.5 parts 1,3-bis-iminoisoindoline in 150 parts by volume methanol and the alkalinity is neutralized by the addition of 6 parts glacial acetic acid. The mixture rapidly acquires an increasing yellow coloration; and the separation of pale yellow small crystals begins at about 35 C. (uniform small needles under the microscope). Stirring is continued for 2 hours at a temperature decreasing from 35% to 20 C., the product is filtered olf with suction, thoroughly washed with methanol and dried in a vacuum at 5070 C. Yield 15.2 parts of straw-yellow small needles of l-(cyano-acetylmethylene)-3-isoindoline, corresponding to about 82% of theory, referred to the S-methyl-isoxazole used.

(b) 4.2 parts 1-(cyano-acetyl-methylene) 3 iminoisoindoline obtained according to Example 45(a) and 2.7 parts Z-amino-benzimidazole are stirred in 40 parts by volume trichlorobenzene at 130l40 C. for 1 hours. After cooling, the mixture is diluted with parts by volume methanol, the product is filtered off with suction and washed with methanol. The resultant dyestuff of the above structural formula can be recrystallized from aqueous dioxan or from nitrobenzene to form orange-colored small leaves and then melts at 302-303 C. (decomp). It dyes polyester fibres according to Examples 2(a) and 2(b) in brown-orange shades.

EXAMPLE 46 (a) 1-[ (cyano-benzirhidazolyl-Z' -methylene]-3-imino- 4,5,6,7-tetrachloro-isoindoline can best be prepared by 1 7 stirring 11.3 parts l-amino-3-imino-4,5,6,7 tetrachloroisoindolenine and 7 parts Z-cyanomethyl-benzimidazole in 80 parts by volume benzyl cyanide at 80 C. for 1 hour and at 100 C. for 5 hours. After cooling, the product is filtered 03 with suction, washed with methanol, and there are thus obtained about 14.5 parts of the monosubstitution product, corresponding ot 86% of theroy, in the form of brownish yellow narrow rhombs of M.P. 360 C. The product dissolves in concentrated sulphuric acid with a golden yellow color and gives orange-yellow flakes in water.

(b) 4.25 parts l-[(cyano-benzimidazolyl-Z')-methylene]-3-imino-4,5,6,7-tetrachloro-isoinodoline obtained according to Example 46(a) and 1.5 parts phenyl-hydrazine are heated under reflux in 50 parts 'by volume of glacial acetic acid for 10 minutes, whereupon the hardly soluble phenyl-hydrazone of the above structural formula results in the form of short red-brown needles. The product dissolves in concentrated sulphur acid with a dirty yellow color, the color of the flakes in water is red-brown. The yield amounts to about 4 parts corresponding to 78% of theory.

EXAMPLE 47 n 11 N\ N NC-i-C no-fg-og 13.00- N c N \NH H m No-ii-cn uo-ii-on 7.5 parts 1,3-diimino-5-methoxy-isoindoline dissolved in 150 parts by volume of 60% aqueous methanol and 6.3 parts Z-cyano-methyl-benzimidazole dissolved in 30 parts by volume methanol are combined and the mixture is stirred at 40 C. for 3 hours. After cooling to C., the product is filtered oil? with suction and washed with 50% methanol. There is obtained a mixture of 1-[(cyano benzimidazaolyl-2')-methylene]-3-imino-5 methoxy isoindoline and 1-[(cyano-benzimidazolyl-2'-)-metihyleue]- 3-imino-6-methoxy-isoindoline. The yield amounts to about 8 parts corresponding to 63% of theory. The product crystallizes from nitrodbenzene or dimethyl formamide in the form of pale yellow small leaves which melt at 360 C. (sintering from about 300 C.). The solutions in pyridine and in concentrated sulphuric acid are 18 EXAMPLE 4s (a) 4.4- parts l,3diimino-5-phenyl-isoindoline and 3.1 parts Z-cyanomethyl-benzimidazo'le are stirred in 30 parts by volume formamide at 60 C. for 1% hours. After cooling, the yellow suspension is diluted with 50 parts by volume of 50% methanol, the product is filtered off with suction and washed with 50% methanol. There are obtained 5 parts, corresponding to 70% of theory, of a dull yellow, non-crystalline monoreaction mixture of l-[(cyano-benzimidazolyl-Z')-methylene]-3-imino-5-phenyl isoindoline and 1-[(cyano-benzimidazolyl-Z')-methylene]-3- imino-6phenyl-isoindoline, which yields a phenyl-hydrazone.

(b) 3 parts of the mixture obtained according to Example 48(a) and 2.5 parts malonie dinitrile are heated in parts by volume methanol under reflux for 6 hours while stirring. After cooling, the orange'colored crystallizate is filtered oil with suction and washed with methanol. The yield amounts to about 3.1 parts, corresponding to 91% of theory, of a mixture according to the above structural formula. A yellowish orange dyeing of good fastness to sublimation is obtained according to Example 2(a) and 2(b) on polyester fibres.

Further examples for the reaction of 1-amino-3-iminoisoindolenine with compounds of the general structure to form the monoreaction product (HI) and then with compounds of the general structure to form the dyestuffs (I) are assembled in the following table. In analogy with Examples '1 and 25, a slight excess is used of 1-amino-3-imino-isoindolenine in the first reaction step and of the component in the second reaction step. Since the components 12 and H can be reacted on l-amino-3-imino-isoindolenine in any sequence, identical dyestuffs may result, as is demonstrated, for example, by the Examples 22 and 64, 24 and 69, 4'1 and 58.

27 and the reaction product of the above structural formula, which crystallizes in the form of orange-red narrow leaflets is filtered off with suction. There are obtained about 6.4 parts corresponding to 76% of theory; M.P. 320325 C. (decomp). Polyester fibre material is dyed according to Example 2(0) in red-orange shades.

EXAMPLE 75 NH i-..

(a) The monosubstitution product used in Paragraph (b) is obtained by stirring a methanolic solution of 1,3- diimino-isoindoline at 20 at most 30 C. with cyanoacetophenone in an amount by to 20% below the theoretical (referred to one mole diimino-isoindoline, i.e. to mole). The l-(cyanobenzoybmethylene)-3- imino-isoindoline which separates in crystalline form after stirring for 2-3 hours, is isolated by filtering olf with suction and washing with methanol, and dried in a vacuum at 60 C. The yield amounts to about 80% of theory, referred to cyano-acetophenone. The microscope shows tufty aggregates of pale yellow needles; the product can be recrystallized from the 90-fold amount of toluene (clearly soluble at boiling temperature) and is then precipitated in the form of shiny golden yellow prisms which exhibit the following melting properties: dipped at 220 C., M.P. 223 C. with grassing; melt resolidifies, becomes very dark upon further heating and does not melt again up to 300 C. Dipped at 200 C. and slowly heated, slow decomposition takes place without melting up to 300 C.

(b) 2.8 parts of crude l-(cyano-benzoyl-methylene)-3- imino-isoindoline obtained according to Paragraph (a) are heated in 50 parts by volume glacial acetic acid at 60 C., and the yellow solution which still contains some undissolved starting material in suspension, is mixed with a solution of 1.1 part phenyl-hydrazine in parts by volume glacial acetic acid. A deep-red (runnings somewhat bluish red) solution is immediately formed and heating is continued at 75-85" C. The l-(cyano-benzioylmethylene)-3-phenyl-hydrazene formed separates in the form of a thick red crystal slurry. Stirring is continued at decreasing temperature for /1 hour, the product is filtered off with suction at 30 C., washed first with glacial acetic acid, then with cyclohexane, and dried in a vacuum at 40 C. Yield 3.2 parts of coarse red needles. According to properties and analysis, the product is a compound of the above structure, which still contains 1 mole acetic acid. When in contact with methanol, the needles change already at room temperature to another shape which contains methanol of crystallization. The phenyl-hydrazene dissolves in a 10% methanolic potassium hydroxide solution with a golden yellow color; the color of the solution changes to an intense red-violet when sufiicient 40% sodium hydroxide solution is added. In 90% sulphuric acid the phenyl-hydrazene dissolves with a brown color. This color of the solution changes to olive-green upon the addition of some potassium persulphate or a little pyrolusite.

3-phonylhydrazones of analogous structure, which have a. red to orange-red color and very good crystallizing power are obtained according to the instruction given above from all the isoindoline derivatives which are described in the present patent specification and contain a substituted methylene group in the 1-position and an imino group in the 3-position.

28 EXAMPLE 76 CONH:

(a) The l (cyano-carbonamido-methylene)-3-iminoisoindoline used as starting material in (b) can be prepared as follows: a solution of 17 parts cyanoacetamide in parts by volume methanol at 45 C. 's added at 20 C. with stirring to a clear solution of 38 parts 1,3-diiminoisoindoline in 250 parts by volume methanol, and stirring is continued without further heat supply (max. temp. 32 C.). Within a few minutes, the solution acquires an intense yellow color and fine yellow small needles are increasingly precipitated. When the precipitated product is isolated by filtering off with suction, washing with methanol and drying at 90 C., then there are obtained, after five hours further stirring, 38 parts of first crystallization=90% of theory, referred to cyanoacetamide. When stirring of the mother liquor is continued over night, then there are obtained a further 3 parts by weight of the same good quality as the first crystallization. The total yield is thus 41 parts=96.5% of theory. The l-(cyanocarbonamido-methylene)-3 imino-isoindoline crystallizes from the 6(H:old amount of formam-ide (heated to a maximum temperature of C.) in the form of brass-yellow shiny fiat prisms or leaflets. When dipped at 285 0., these become dark and exhibit a melting point of about 290 C. with gassing.

(b) 21.1 parts 1 (cyano-carbonamido-methylene)-3- iminoisoindoline (prepared according to Paragraph (a)) are dissolved in 600 parts by volume dirnethyl formamide C. and a solution of 13.5 parts (5% more than the theoretical amount) of barbituric acid in 100 parts by volume dirnethyl formamide heated to 50-60 C. is stirred into the above solution. The initially clear yellow solution mixture rapidly becomes cloudy and the resultant conden sation product of the above structure is separated in the form of a very finely crystalline yellow crystal slurry. Stirring is continued at 90 C. for 15 minutes; the product is filtered off with suction while warm, briefly washed twice with dirnethyl formamide and subsequently with methanol or water, and dried at 90-l00 C.

Yield 21-22 parts of a clear yellow soft-grained powder which is insoluble in the usual solvents for lacquers and even in boiling nitrobenzene. When used as a yellow pigment, it yields clear yellow lacquer coatings of good fastness properties.

EXAMPLE 77 NC CONH| 'described in Paragraph (b) and used as stirred in 200 parts dimethyl sulphoxide with 11 parts malonic dinitrile and the mixture is heated. A clear solution begins to form already at 50-60" C. the yellow color of which becomes more and more reddish as the temperature rises up to about 110 C. 50 parts glacial acetic acid are added and stirring is continued at 100 C. for minutes. The mixture is subsequently diluted, while slowly stirring, with a mixture of 200 parts of water, 50 parts glacial acetic acid and 300 parts by volume methanol, a final temperature of about C. being achieved by cooling. During the diluting operation, the golden yellow condensation product crystallizes (in the form of clusters of coarse prisms when examined under the microscope). Yield of l-(cyanocarbonamido-methylene) 3 (biscyano-methylene)-isoindoline: 24.5 parts- 94% of theory.

In contradistinction to the product, this compound no longer yields red phenyl-hydrazone when heated with phenylhydrazine in glacial acetic acid. It readily dissolves in cold pyridine and subsequently recrystallizes as an orange-colored pyridine salt. When the suspension of the pyridine salt is dissolved with plenty of hot water, then a yellow solution is formed from which polyamide fibres are dyed in intense and clear yellow shades.

EXAMPLE 78 (a) The l-(bis-cyano-methylene)-3 imino-isoindoline starting material is prepared from a methanolic solution of 1,3-bis-iminoisoindoline with the addition of a molar amount of malo nic dinitrile at room temperature. Immediately after the addition of the malonic dinitrile, a finely crystalline pale yellowish precipitation occurs. If necessary, the suspension is sufficiently diluted with methanol to remain homogeneously stirrable. After further stirring for 10 minutes, the reaction 'is already completed at room temperature. Water is added in an amount of 50% by volume of the suspension, the product is filtered off with suction, thoroughly washed with water and dried in a vacuum at 60 C. Yield about 95% of theory in form of a slightly yellowish finely crystalline powder which is only barely soluble 'in glacial acetic acid and hydrocarbons, even in the hot.

It is partially dissolved in dimethyl formamide at room temperature but recrystallizes within a short time in the form of a thick slurry of pale yellow solvated crystals. It clearly dissolves in warm dimethyl formamide with an intense yellow color. In dimethyl sulphoxide, it gives a clear stable solution already at room temperature. Even if the preparation is carried out with 2 moles malonic nitrile per mole bis-imino-isoindoline, and 1 mole glacial acetic acid is added to the solvent methanol (in order to accelerate the reaction to form 1,3-bis-(dicyano-methylene)-iso'indoline) and the mixture is heated at boiling temperature under reflux for 4 hours, the amount of product isolated by suction-filtration still consists of the pure monoreaction product described above (about 43% of theory), since the l,3-bis-(dicyano-methylene)-isoindoline "formed (in a yield of about 45%) remains dissolved with a deep orange-yellow color in the ammoniacal methanol "filtrate from which it separates in the form of orangeyellow flakes only upon acidification. The 1,3-bis-(dicya- A no-methylene)-isoindoline (structure as illustrated) is obtained in the form of golden yellow shiny small needles by dissolving in the six-fold volume of dimethyl formamide at 50 C., diluting with the same volume of methanol and cooling. It dissolves already in a dilute hot sodium carbonate solution with a yellow color and in cold pyridine with a red-orange color and decomposes with gassing-after dipping at 320 C.only above 350 C. In contradistinction to the monoreaction product described above, it gives no phenyl-hydrazone derivative with phenylhydrazine in boiling glacial acetic acid.

(b) 9.7 parts 1-(bis-cyano-m.ethylene)-3-iminoisoindoline (prepared according to Paragraph (a) are finely dispersed in glacial acetic acid and, after the addition of 8 ,parts o-nitrophenyl-hydrazine, heated at boiling tempera- ON ON In a 25% methanolic potassium hydroxide solution, a characteristic deep blue-green solution is partially formed, besides crystallized potassium salt. The 2,4-dinitrophenyl-hydrazone derivative of analogous structure (prepared from the same starting material with approximately molar amounts of 2,4dinitrophenyl-hydrazine in glycol by briefly heating to 180 C.) is very similar to the 2-nitrophenyl-hydrazone derivative described above in respect of its intrinsic color and the crystal form, but it gives a blueviolet solution with a 10% methanolic potassium hydroxide solution, whereas it is hardly soluble in a 25% methanolic potassium hydroxide solution. The correspond ing unsubstituted phenyl-hydrazone derivativeyellowish red fine prisms, M.P. and decomp. p. 253-256" C.-readily dissolves in a 10% as well as in a 25% methanolic potassium hydroxide solution. These solutions are both red-orange in a thick layer and greenish yellow in a very thin layer.

EXAMPLE 79 CN cooou:

reacted with hydrazine in glacial acetic acid.

(a) A solution of 99 parts cyanoacetic acid methyl ester in 100 parts methanol is slowly poured at 20 C., with stirring and external cooling with water, into a clear possibly filtered, solution of 200 parts of 94.5% 1,3-bisimino-isoindoline (corresponding to one mole of pure product +30% excess), within a period of time which enables a temperature of 20 C. to be maintained. During the addition of the ester, the solution first turns yellowish, but soon a pale yellow, thick, finely crystalline precipitate occurs. After further stirring for 2 hours, the reaction is already completed at 20 C. The product is filtered 01f with suction, washed first with 250 parts methanol and subsequently thoroughly with water. After drying in a vacuum, there are obtained 184.5 parts of an only slightly yellowish, finely crystalline powder which, according to analysis and properties, is almost pure l-(cyano-carbomethoxy-methylene)-3-imino isoindoline. 184.5 parts correspond to about 62% of theory, referred to the bis-imino-isoindoline used (in excess) or to 92% of the theoretical amount of 227 parts, referred to cyanoacetic ester. The product can be recrystallized from the 70-fold amount of methanol and is then obtained in the form of slightly yellow needles. The melting properties of the recrystallized product do not differ from those of the crude product. Samples of both products, dipped in melting point tubes at 195 C., change via orange to brown-black and decompose with gassing at 202203 C.

If in the reaction described above, the starting materials are used in a molar ratio of about 1:1 and the process is otherwise carried out in the same manner, then the resultant crude product already contains or more percent of 1,3-bis-(cyano-carbomethoxy-methylene)-isoindoline. The amount of this byproduct, moreover, increases as the reaction temperature rises and upon the addition of glacial acetic acid. The bis-reaction product becomes the predominant main product when 2 moles cyanoacetic acid ester are used per mole 1,3-diimino-isoindoline. It crystallizes from glacial acetic acid or chlorobenzene in the form of yellow shiny prisms of decomposition point 285287 C. and can be most rapidly distinguished from the monoreaction product described above by the fact that it yields no red-orange reaction product when heated in glacial acetic acid with some phenyl-hydrazine.

(b) 11.4 parts l-(cyano-carbomethoXy-methylene)-3- imino-isoindoline (prepared according to Paragraph (a)) are heated in 250 parts by volume glacial acetic acid until the material dissolved at about 65 C. 5 parts of a 25% hydrazine hydrate solution are then slowly added with stirring, whereupon the color first changes to orange, and, finally, orange-colored small crystals are increasingly precipitated. Heating is continued at boiling temperature for 2-5 minutes, the mixture is allowed to cool to 20 C., the product is filtered off with suction, washed with glacial acetic acid, then with methanol and finally with water, and dried at 901 00 C. The yield of light orange-colored small needles is"9.55 parts=83.5% of the starting material. The product crystallizes from dimethyl formamide in the form of long red-orange needles and has a decomposition point of 315 C. It is insoluble in hot methanol; when a small amount of a 40% sodium hydroxide solution is added, it gives a carmino-red solution from which a violet Na-salt crystallizes upon cooling.

(c) The l-(cyano-carboethoxy-methylene)-3-imino-isoindoline prepared in analogy with Paragraph (a) but with cyanoacetic acid ethyl ester, can be obtained in a similarly good yield, ifbecause of the greater solubility of the ethyl ester--the crystal slurry is concentrated after the reaction to about half its volume. The crude product has a decomposition point of 155160 C. It can be recrystallized from the 25-fold amount of benzene, whereupon coarse shiny prisms crystallize out, which lose their gloss when dried. The decomposition point of the pure product is 161-162 C. after change of color to orange to dark brown.

32 EXAMPLE (a) The 1-[1'-phenyl-3'-methyl-5-oxo) -pyrazolidene- 4'1-3-imino-isoindoline used in Paragraph (b) is prepared by adding a solution of 17.4 parts 1-phenyl-3-methyl-pyrazolone-(S) in parts by volume methanol heated to 30 C. to a solution of 21 parts 1,3-diimino-isoindoline (45% excess) in 200 parts by volume methanol at a maximum temperature of 30 C., while stirring. The mixture acquires a deep brownish red color (dull yellowish to orange in a thin layer) and crystals of vitrous lustre begin to separate after a few minutes (fiat rhombs or prisms by weak magnification under the microscope, red-orange by transmitted light). Working up is carried out by filtering 011 with suction at 15-18 C., washing with a little cold methanol and drying in a vacuum at 50 C. Yield of glassy crystals which are red-orange by transmitted light and contain 1 mole methanol of crystallization: 29.0 parts=87% of the theoretical amount of 33.4 parts.

(b) 33.4 parts 1-[(l'-phenyl-3'-methyl-5-oxo)-pyrazolidene-4']-3-imino-isoindoline containing 1 mole methanol of crystallization (prepared according to Paragraph (a) are heated in 600 parts by volume glacial acetic acid at 1l0'C. whereupon the product dissolves with a yellowbrown colour. When 13 parts phenyl-hydrazine are then added, the solution becomes dark-red, and brownish red small prisms crystallise within one minute to form a thick slurry. Heating is continued at boiling temperature for about 10 minutes, the product is filtered off with suction when cold, washed once with glacial acetic acid, then thoroughly with water, and dried at 100 C. Yield is 30 parts==77% of the theoretical amount of 39.3 parts. Melting point (dipped at C.) is 191 C., with decomposition. The product clearly dissolves in the 15-fold amount of hot toluene. When this solution is diluted with twice its volume of methanol, then the phenyl-hydrazone derivative is precipitated with one mole methanol in the form of long fiat brownish-red crystals having a slight brassy lustre. The decomposition point (dipped at 185 C.), is 194-195 C. The solution in concentrated sulphuric acid is initially red-violet, rapidly changing to carmine red. The likewise red-violet solution in 85% sulphuric acid turns dull blue and finally green upon the addition of pyrolusite.

EXAMPL'E 81 (a) l-(2',4' dinitro phenyl hydrazono)-3-iminoisoindoline can be obtained in the usual manner from 10 parts 2,4-dinitro-phenyl-hydrazine and 12 parts of 96.5% 1-arnino-3-imino-isoindolenine in 50 parts by volume formamide at 60 C. Yield is 15 parts=91% of theory.

(b) 3.3 parts l-(2',4 dinitro phenyl-hydrazono)-3- imino-isoindoline obtained according to Example 81(a) and 1.3 parts malonic dinitrile are heated in 50 parts by volume nitrobenzene at ZOO-210 C. for 10 minutes. The reaction product of the structure as illustrated which 32 Aswxwxsm no aws n sz Z Z mw 3 3 O \OIZJH 55:; nawvwvm 98 3 Z 8 8 fil 6 .NOIO/ \O Z-m 3 2 2 62 2:55am 8 SE B EZ mo 3 8 0/ Q \OIZSH a gm a @1252: 8 swiiv n z z 3: 2 32 mg 2 Ags E eafi fi Eveoo mo ooodfi a: 2 8 2. Z \012 a f 5:52am m3 ae n bi i6o QmoTo QmoTooo mo oz 2: m u :....:.8 Z ETD: mw w m Z 5,2 Aovm ow AomC QGQNHSQESZ JHOI|IHHO|ZNHH A vnm HH 5m m m oooo w 2: a f EN 8 8g E a 35 5a z z 5mm E Q 2 E5 5 5 c8 3 6 3 3 2 2 m m m E2 2 a g K i MW .283 m .EmQEm M m MHZ 53H 0 o ADV m2 SF O .M

V HMO v O Z H H H mw Z x523? Aemx vm ow ow 212 mu nmuolq illw O 7 a 3 .5 $3 s 22 fl ww 1 mm f a J 23 x3 0 A vm Ken 3 ow n Q O O L mm J l im m O O Z WH Z V HHU JU O z OZ Z 2 521 M A vm ow 0% m nmm o l lw 5 0 .Z O nw z m F 6Q GK mw 12%.... 2'2 no 93 mm Scam O HH O HHO JMW mw z m 2 A3 35 ii 8 83 3355222 III 8 935mg S .1 SEER/ 3 i L 25 S om m .l w 3 ADC 62; 8 E EQQQ HH 39 We claim: 1. The compounds of the formula Hill 40 wherein X and X are 0, S, or NH, however, both not identical.

References Cited UNITED STATES PATENTS 5 3,499,908 3/1970 Vollman et a1 260-305 3,646,033 2/1972 Leister et a1 260305 RICHARD J. GALLAGHER, Primary Examiner US. (:1. X.R. 

